EP0012283B1 - Process for preparing basic dyestuffs - Google Patents

Process for preparing basic dyestuffs Download PDF

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Publication number
EP0012283B1
EP0012283B1 EP79104781A EP79104781A EP0012283B1 EP 0012283 B1 EP0012283 B1 EP 0012283B1 EP 79104781 A EP79104781 A EP 79104781A EP 79104781 A EP79104781 A EP 79104781A EP 0012283 B1 EP0012283 B1 EP 0012283B1
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Prior art keywords
alkyl
phenyl
atoms
substituted
radical
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German (de)
French (fr)
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EP0012283A1 (en
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Karl Heinz Dr. Hermann
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Bayer AG
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Bayer AG
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B11/00—Diaryl- or thriarylmethane dyes
    • C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
    • C09B11/10—Amino derivatives of triarylmethanes
    • C09B11/12—Amino derivatives of triarylmethanes without any OH group bound to an aryl nucleus
    • C09B11/18—Preparation by oxidation
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B11/00—Diaryl- or thriarylmethane dyes
    • C09B11/02—Diaryl- or thriarylmethane dyes derived from diarylmethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B11/00—Diaryl- or thriarylmethane dyes
    • C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
    • C09B11/26—Triarylmethane dyes in which at least one of the aromatic nuclei is heterocyclic

Definitions

  • alkyl radicals are to be understood in particular as C 1 -C 4 alkyl radicals.
  • the alkyl radicals carry, for example, 1-3 of the nonionic or acidic substituents. Halogen, hydroxy, C 1 -C 4 -alkyl, cyano, C 1 -C 4 -alkoxy, C 1 -C 4 -alkoxycarbonyl, C 1 -C 3 -alkylcarbonyloxy, aminocarbonyl, sulfo or carboxy are to be mentioned as such .
  • Halogen is preferably to be understood as fluorine, chlorine or bromine.
  • Suitable aryl radicals are in particular an optionally substituted phenyl or naphthyl radical.
  • Suitable aralkyl radicals are in particular an optionally substituted benzyl, ⁇ - or ⁇ -phenylethyl, ⁇ -, ⁇ - or ⁇ -phenylpropyl radical.
  • isocycles can carry, for example, 1-3 substituents such as halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, sulfo or carboxyl.
  • heteroaromatic ring D the indolyl-3, pyrazolyl-4 and pyrazolinon-5-yl-4 ring may be mentioned in particular.
  • the heterocyclic rings are e.g. B. substituted by C 1 -C 4 alkyl groups or phenyl.
  • the anions are derived from inorganic or organic acids and are generally given by the production process and the cleaning of the crude dye which may have been carried out.
  • the dyes are present as double zinc chloride salts, acetates, methosulfates, ethosulfates or as halides (in particular as chlorides or bromides).
  • the anions can be exchanged for other anions in a known manner.
  • the quinones used as oxidizing agents can be: tetrachloro-, tetrabromo-, tetrafluoro-, tetracyane-, dicyandichloro-1,4-benzoquinone, tetrachloro- or tetrabromo-1,2-benzoquinone, 2-nitro-, 2,7-dinitro- or 4,5-dinitrophenanthrenequinone. Tetrachloro- or tetrabromo-1,4-benzoquinone are preferred.
  • the quinones are used in an amount of 10- 3 to 10- 1 mol based on the molar amount of compound III. Instead of the quinones, the corresponding hydroquinones can also be used.
  • the new process is carried out by dissolving or suspending compounds of the general formula III in a neutral or acidic, aqueous or organic solvent at temperatures between 0 ° C. and 150 ° C., preferably between 20 and 70 ° C., 10 - 3 to 10 -1 mol of quinone, based on the molar amount of compound 111, are added, the reaction solution is mixed intensively with supplied oxygen, normally pure oxygen or air, and either 1 to 20 mol% of nitrates or nitrites are added in the course of the reaction, or 1 to 20 in total Mol percent nitrogen oxides added.
  • the metering can take place either with the oxygen flow or from a separate metering device. In order to achieve a high reaction rate, intensive mixing of gas and liquid is necessary. Working under pressure is also possible.
  • German patent specification 2 31 992 discloses the production of dyes from the triphenylmethane series by oxidation of leuco compounds with nitrosylsulfuric acid.
  • a mixture of 109.5 parts of the compound of the formula 300 parts of glacial acetic acid, 300 parts of chlorobenzene and 6 parts of chloranil are gassed with air at 50 ° C.
  • a total of 1.2 parts of a mixture of nitrogen monoxide and nitrogen dioxide are metered in continuously during the reaction.
  • the chlorobenzene and part of the glacial acetic acid are evaporated off in vacuo, the residue is taken up in hot H 2 O, acidified with dilute hydrochloric acid, filtered hot and precipitated with sodium chloride.
  • the dye is obtained in 90% yield. Similar results are obtained if sodium nitrite or iron (III) nitrate is used as the catalyst instead of the nitrogen oxides.
  • a suspension of 31.8 parts of the compound of the formula 1 part of chloranil and 450 parts of water are treated with oxygen at 70 ° C. with vigorous stirring.
  • a total of 0.5 part of a mixture of nitrogen monoxide and nitrogen dioxide is metered in continuously during the reaction.
  • 88% of the starting compound used is oxidized to the dye.
  • the dye can be isolated by treating the reaction solution with sodium chloride. Similar results are obtained if sodium nitrite or iron (III) nitrate are used as catalysts instead of the nitrogen oxides.
  • leuco compounds can also be oxidized in good yield by the process according to the invention.

Description

Die Erfindung betrifft ein Verfahren zur Herstellung basischer Farbstoffe der allgemeinen Formel

Figure imgb0001
in der

  • A und B unabhängig voneinander für einen heteroaromatischen Rest oder einen Rest der allgemeinen Formel
    Figure imgb0002
    stehen, in der
  • Ar die Gruppierungen
    Figure imgb0003
    in denen
  • Y für Wasserstoff oder nichtionische Substituenten und
  • n für die Zahlen 1 bis 4 stehen, bedeutet und
  • R1 und R2 für Wasserstoff oder gegebenenfalls durch nichtionische oder saure Gruppen substituiertes Alkyl, Aryl, Cyclohexyl oder Aralkyl stehen oder zusammen oder mit der o-Position von Ar einen heterocyclischen Ring bilden, der durch C1-C4-Alkyl oder Phenyl substituiert sein kann,
  • D Wasserstsoff, Alkyl, gegebenenfalls mit neutralen oder sauren Gruppen substituiertes Aryl oder einen heteroaromatischen Rest bedeutet und
  • X für ein Anion steht,

dadurch gekennzeichnet, daß man Verbindungen der allgemeinen Formel
Figure imgb0004
in der
  • A, B und D die oben genannte Bedeutung haben,
    mit Sauerstoff in Gegenwart katalytischer Mengen von durch Halogen oder Cyan substituierten Benzochinonen oder durch Nitro substituierten Phenanthrenchinonen und in Gegenwart katalytischer Mengen von Stickstoffoxiden - ausgenommen Distickstoffmonoxid - der von Substanzen, die unter den Reaktionsbedingungen solche Stickstoffoxide erzeugen, oxidiert.
The invention relates to a process for the preparation of basic dyes of the general formula
Figure imgb0001
 in the
  • A and B independently of one another for a heteroaromatic radical or a radical of the general formula
    Figure imgb0002
     stand in the
  • Ar the groupings
    Figure imgb0003
     in which
  • Y represents hydrogen or nonionic substituents and
  • n stands for the numbers 1 to 4, means and
  • R 1 and R 2 represent hydrogen or alkyl, aryl, cyclohexyl or aralkyl optionally substituted by nonionic or acidic groups or together or with the o-position of Ar form a heterocyclic ring which is substituted by C 1 -C 4 alkyl or phenyl can be,
  • D represents hydrogen, alkyl, aryl optionally substituted with neutral or acidic groups or a heteroaromatic radical and
  • X represents an anion,

characterized in that compounds of the general formula
Figure imgb0004
 in the
  • A, B and D have the meaning given above,
    oxidized with oxygen in the presence of catalytic amounts of benzoquinones substituted by halogen or cyano or phenanthrene quinones substituted by nitro and in the presence of catalytic amounts of nitrogen oxides - with the exception of nitrous oxide - of substances which generate such nitrogen oxides under the reaction conditions.

In den Formeln sind unter Alkylresten insbesondere C1-C4-Alkylreste zu verstehen. Die Alkylreste tragen beispielsweise 1-3 der nichtionischen oder sauren Substituenten. Als solche sind Halogen, Hydroxy, C1-C4-Alkyl, Cyan, C1-C4-Alkoxy, C1-C4-Alkoxycarbonyl, C1-C3-A!kylcarbonyloxy, Aminocarbonyl, Sulfo oder Carboxy zu nennen.In the formulas, alkyl radicals are to be understood in particular as C 1 -C 4 alkyl radicals. The alkyl radicals carry, for example, 1-3 of the nonionic or acidic substituents. Halogen, hydroxy, C 1 -C 4 -alkyl, cyano, C 1 -C 4 -alkoxy, C 1 -C 4 -alkoxycarbonyl, C 1 -C 3 -alkylcarbonyloxy, aminocarbonyl, sulfo or carboxy are to be mentioned as such .

Unter Halogen ist vorzugsweise Fluor, Chlor oder Brom zu verstehen.Halogen is preferably to be understood as fluorine, chlorine or bromine.

Geeignete Arylreste sind isbesondere ein gegebenenfalls substituierter Phenyl- oder Naphtylrest.Suitable aryl radicals are in particular an optionally substituted phenyl or naphthyl radical.

Geeignete Aralkylreste sind insbesondere ein gegebenenfalls substituierter Benzyl-, α- oder β-Phenyläthyl-, χ-, β- oder γ-Phenylpropylrest.Suitable aralkyl radicals are in particular an optionally substituted benzyl, α- or β-phenylethyl, χ-, β- or γ-phenylpropyl radical.

Diese Isocyclen können beispielsweise 1-3 Substituenten wie Halogen, C1-C4-Alkyl, C1-C4-alkoxy, Sulfo oder Carboxyl tragen.These isocycles can carry, for example, 1-3 substituents such as halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, sulfo or carboxyl.

Die Reste R1 und R2 bilden zusammen oder mit der o-Position von Ar z. B. 5- oder 6gliedrige Ringe; zusammen bilden sie beispielsweise einen Piperidin-, Pyrrolidin-, Morpholin- oder Piperazin-Ring; mit der o-Position von Ar bilden sie zusammen beispielsweise einen Tetrahydrochinolin-, Indolin-, Julolidin-, Phenmorpholin-, Tetrahydrochinoxalin- oder Carbazol-Ring.The radicals R 1 and R 2 together or with the o-position of Ar z. B. 5- or 6-membered rings; together they form, for example, a piperidine, pyrrolidine, morpholine or piperazine ring; together with the o-position of Ar they form, for example, a tetrahydroquinoline, indoline, julolidine, phenmorpholine, tetrahydroquinoxaline or carbazole ring.

Als heteroaromatischen Ring D seien vor allem der Indolyl-3-, Pyrazolyl-4- und Pyrazolinon-5-yl-4-Ring genannt. Die heterocyclischen Ringe sind z. B. durch C1-C4-Alkyl-Gruppen oder Phenyl substituiert.As the heteroaromatic ring D, the indolyl-3, pyrazolyl-4 and pyrazolinon-5-yl-4 ring may be mentioned in particular. The heterocyclic rings are e.g. B. substituted by C 1 -C 4 alkyl groups or phenyl.

Unter den oben beschriebenen Farbstoffen lassen sich besonders solche der allgemeinen Formel IV gut darstellen,

Figure imgb0005
in der unabhängig voneinander

  • R3 und R5 Wasserstoff, C1-C4-Alkyl, Hydroxyalkyl mit zwei und drei C-Atomen, Cyanäthyl, Alkoxyalkyl mit insgesamt drei bis fünf C-Atomen, Alkoxycarbonylalkyl mit insgesamt drei bis fünf C-Atomen, Alkoxycarbonylalkyl mit insgesamt drei bis acht C-Atomen, Alkylcarbonyloxyalkyl mit insgesamt drei bis acht C-Atomen, Ci- bis C4-Halogenalkyl, Sulfoalkyl mit zwei bis vier C-Atomen, Cyclohexyl, Benzyl, Phenyl, Phenäthyl, durch Halogen, Cl- bis C4-Alkyl oder -Alkoxy substituiertes Phenyl oder Sulfobenzyl,
  • R4 und R6 C1- bis C4-Alkyl, Hydroxyalkyl mit zwei oder drei C-Atomen, Cyanäthyl, C1- bis C4-Halogenalkyl, Alkoxyalkyl mit insgesamt drei bis fünf C-Atomen, Alloxycarbonylalkyl mit insgesamt drei bis acht C-Atomen, Alkylcarbonyloxyalkyl mit insgesamt drei bis acht C-Atomen oder Benzyl

bedeuten, oder
  • R3 und R4 und/oder R5 und R6 zusammen einen gegebenenfalls durch C1-C4-Alkyl substituierten Pyrrolidin-, Piperidin-, Morpholin- oder Piperazin-Ring oder
  • R3, R4, R5 und/oder R6 mit der o-Position des Phenylringes verbunden sind und dann mit dem Phenylring zusammen einen gegebenenfalls durch C1-C4-Alkyl, Phenyl oder Benzyl substituierten Tetrahydrochinolin-, Indolin-, Julolidin-, Phenmorpholin-, Tetrahydrochinoxalin- oder Carbazol-Ring bilden,
  • R7 und R8 für Wasserstoff, C1- bis C4-Alkyl, C1- bis C4-Alkoxy, Carbonsäure oder Halogen stehen,
  • n eine ganze Zahl zwischen 1 und 4 bedeutet und
  • E Phenyl, durch Halogen, Ci- bis C4-Alkyl, Cl- bis C4-Alkoxy, Nitro, die Carboxyl- oder Sulfonsäuregruppe mono- oder di-substituiertes Phenyl oder Naphthyl, einen heterocyclischen Rest der allgemeinen Formel
    Figure imgb0006
    in der
  • Rg H, Cl-C4-Alkyl, Phenyl, Carbonsäure-C1- oder C2-alkylester, gegebenenfalls durch C1-C4-Alkyl N-substituiertes Carbonsäureamid oder C1-C4-Alkoxy bedeuten, einen Rest der allgemeinen Formeln
    Figure imgb0007
    und
    Figure imgb0008
    in denen
    • n, R3, R4 und R7 die oben genannte Bedeutung haben,
  • oder einen Rest der allgemeinen Formeln
    Figure imgb0009
    und
    Figure imgb0010
    in denen
    • R10 Wasserstoff, C1 ― C4-Alkyl oder Halogen, insbesondere Chlor oder Brom, und n, R3, R4, R5, R6, R7 und R8 die obengenannte Bedeutung haben, und
    • X für ein Anion
    • steht.
  • Als Ausgangsmaterialien zur Darstellung der Farbstoffe der allgemeinen Formel IV verwendet man Verbindungen der allgemeinen Formel
    Figure imgb0011
    in der
    • n und R3 bis R8 die oben genannte Bedeutung haben und
    • F gleich E ist oder ein Rest der allgemeinen Formeln
      Figure imgb0012
      und
      Figure imgb0013
      in denen
    • n, R3 bis R8 und R10 die oben genannte Bedeutung haben.
Among the dyes described above, those of the general formula IV can be particularly well represented
Figure imgb0005
 in the independently of each other
  • R 3 and R 5 are hydrogen, C 1 -C 4 alkyl, hydroxyalkyl with two and three C atoms, cyanoethyl, alkoxyalkyl with a total of three to five C atoms, alkoxycarbonylalkyl with a total of three to five C atoms, alkoxycarbonylalkyl with a total of three up to eight carbon atoms, alkylcarbonyloxyalkyl with a total of three to eight carbon atoms, C i - to C 4 -haloalkyl, sulfoalkyl with two to four carbon atoms, cyclohexyl, benzyl, phenyl, phenethyl, by halogen, C 1 - to C 4- alkyl or alkoxy-substituted phenyl or sulfobenzyl,
  • R 4 and R 6 C 1 - to C 4 alkyl, hydroxyalkyl with two or three C atoms, cyanoethyl, C 1 - to C 4 haloalkyl, alkoxyalkyl with a total of three to five C atoms, alloxycarbonylalkyl with a total of three to eight C atoms, alkylcarbonyloxyalkyl with a total of three to eight C atoms or benzyl

mean or
  • R 3 and R 4 and / or R 5 and R 6 together form a pyrrolidine, piperidine, morpholine or piperazine ring which is optionally substituted by C 1 -C 4 alkyl or
  • R 3 , R 4 , R 5 and / or R 6 are connected to the o-position of the phenyl ring and then together with the phenyl ring an optionally substituted by C 1 -C 4 alkyl, phenyl or benzyl tetrahydroquinoline, indoline, julolidine -, phenmorpholine, tetrahydroquinoxaline or carbazole ring form,
  • R 7 and R 8 are hydrogen, C 1 - to C 4 -alkyl, C 1 - to C 4 -alkoxy, carboxylic acid or halogen,
  • n is an integer between 1 and 4 and
  • E phenyl, by halogen, C i - to C 4 -alkyl, C l - to C 4 -alkoxy, nitro, the carboxyl or sulfonic acid group mono- or di-substituted phenyl or naphthyl, a heterocyclic radical of the general formula
    Figure imgb0006
     in the
  • Rg is H, C 1 -C 4 alkyl, phenyl, carboxylic acid C 1 - or C 2 alkyl esters, optionally substituted by C 1 -C 4 alkyl N-substituted carboxamide or C 1 -C 4 alkoxy, a rest of the general formulas
    Figure imgb0007
     and
    Figure imgb0008
     in which
    • n, R 3 , R 4 and R 7 have the meaning given above,
  • or a rest of the general formulas
    Figure imgb0009
     and
    Figure imgb0010
     in which
    • R 10 is hydrogen, C 1 - C 4 alkyl or halogen, in particular chlorine or bromine, and n, R 3 , R 4 , R 5 , R 6 , R 7 and R 8 have the abovementioned meaning, and
    • X for an anion
    • stands.
  • Compounds of the general formula are used as starting materials for the preparation of the dyes of the general formula IV
    Figure imgb0011
     in the
    • n and R 3 to R 8 have the meaning given above and
    • F is E or a radical of the general formulas
      Figure imgb0012
       and
      Figure imgb0013
       in which
    • n, R 3 to R 8 and R 10 have the meaning given above.

Besonders bevorzugt sind solche Farbstoffe der allgemeinen Formel IV, in der unabhängig voneinander

  • R3 und R5 für Wasserstoff, Methyl, Äthyl, Oxäthyl, Propyl oder Butyl,
  • R4 und R6 für Methyl, Äthyl, Sulfobenzyl oder Sulfoäthyl,
  • R7 und R8 für Wasserstoff, Methyl, Methoxy oder Chlor,
  • E für Phenyl, durch Chlor, Methoxy oder die Sulfonsäuregruppe substituiertes Phenyl, p-Dimethylaminophenyl, p-Diäthylaminophenyl, p-Bisoxäthylaminophenyl oder den Rest der allgemeinen Formel V mit
  • Rg für Wasserstoff, Methyl oder Phenyl und
  • R3 für Methyl und Phenyl, stehen.
Those dyes of the general formula IV in which are independent of one another are particularly preferred
  • R 3 and R 5 represent hydrogen, methyl, ethyl, oxethyl, propyl or butyl,
  • R 4 and R 6 are methyl, ethyl, sulfobenzyl or sulfoethyl,
  • R 7 and R 8 are hydrogen, methyl, methoxy or chlorine,
  • E for phenyl, phenyl substituted by chlorine, methoxy or the sulfonic acid group, p-dimethylaminophenyl, p-diethylaminophenyl, p-bisoxethylaminophenyl or the rest of the general formula V with
  • Rg for hydrogen, methyl or phenyl and
  • R 3 represents methyl and phenyl.

Die Anionen leiten sich von anorganischen oder organischen Säuren ab und sind im allgemeinen durch das Herstellungsverfahren und die evtl. vorgenommene Reinigung des rohen Farbstoffes gegeben. Im allgemeinen liegen die Farbstoffe als Zinkchlorid-Doppelsalze, Acetate, Methosulfate, Äthosulfate oder als Halogenide (insbesondere als Chloride oder Bromide) vor. Die Anionen können in bekannter Weise gegen andere Anionen ausgetauscht werden.The anions are derived from inorganic or organic acids and are generally given by the production process and the cleaning of the crude dye which may have been carried out. In general, the dyes are present as double zinc chloride salts, acetates, methosulfates, ethosulfates or as halides (in particular as chlorides or bromides). The anions can be exchanged for other anions in a known manner.

Die als Oxidationsmittel eingesetzten Chinone können sein: Tetrachlor-, Tetrabrom-, Tetrafluor-, Tetracyan-, Dicyandichlor-1,4-benzochinon, Tetrachlor- oder Tetrabrom-1,2-benzochinon, 2-Nitro-, 2,7-Dinitro- oder 4,5-Dinitrophenanthrenchinon. Bevorzugt werden Tetrachlor- oder Tetrabrom-1,4-benzochinon. Man setzt die Chinone in einer Menge von 10-3 bis 10-1 Mol bezogen auf die Molmenge der Verbindung III ein. Anstelle der Chinone können auch die entsprechenden Hydrochinone eingesetzt werden.The quinones used as oxidizing agents can be: tetrachloro-, tetrabromo-, tetrafluoro-, tetracyane-, dicyandichloro-1,4-benzoquinone, tetrachloro- or tetrabromo-1,2-benzoquinone, 2-nitro-, 2,7-dinitro- or 4,5-dinitrophenanthrenequinone. Tetrachloro- or tetrabromo-1,4-benzoquinone are preferred. The quinones are used in an amount of 10- 3 to 10- 1 mol based on the molar amount of compound III. Instead of the quinones, the corresponding hydroquinones can also be used.

Geeignete Katalysatoren sind:

  • Stickstoffoxid oder Stickstoffdioxid oder Substanzen, die unter den Reaktionsbedingungen - vor allen Dingen in sauren Lösungsmitteln - Stickstoffoxide freisetzen, z. B. Eisen-III-nitrat oder Natriumnitrit. Die Katalysatoren werden in Konzentrationen von 1 bis 20 Molprozent, bezogen auf das Substrat, angewandt.
Suitable catalysts are:
  • Nitric oxide or nitrogen dioxide or substances that release nitrogen oxides under the reaction conditions - especially in acidic solvents, e.g. B. iron III nitrate or sodium nitrite. The catalysts are used in concentrations of 1 to 20 mole percent, based on the substrate.

Man führt das neue Verfahren so durch, daß man in einem neutralen oder sauren, wäßrigen oder organischen Lösungsmittel Verbindungen der allgemeinen Formel III bei Temperaturen zwischen 0°C und 150° C, bevorzugt zwischen 20 und 70° C, löst oder suspendiert, 10 -3 bis 10-1 Mol Chinon, bezogen auf die Molmenge der Verbindung 111, zugibt, die Reaktionslösung intensiv mit zugeführten Sauerstoff, normalerweise Reinsauerstoff oder Luft, vermischt und im Verlauf der Reaktion entweder 1 bis 20 Molprozent Nitrate oder Nitrite zugibt oder insgesamt 1 bis 20 Molprozent Stickstoffoxide zudosiert. Die Zudosierung kann entweder mit dem Sauerstoffstrom oder aus einer separaten Dosiervorrichtung erfolgen. Um eine hohe Reaktionsgeschwindigkeit zu erreichen, ist eine intensive Durchmischung von Gas und Flüssigkeit notwendig. Das Arbeiten unter Druck ist auch möglich.The new process is carried out by dissolving or suspending compounds of the general formula III in a neutral or acidic, aqueous or organic solvent at temperatures between 0 ° C. and 150 ° C., preferably between 20 and 70 ° C., 10 - 3 to 10 -1 mol of quinone, based on the molar amount of compound 111, are added, the reaction solution is mixed intensively with supplied oxygen, normally pure oxygen or air, and either 1 to 20 mol% of nitrates or nitrites are added in the course of the reaction, or 1 to 20 in total Mol percent nitrogen oxides added. The metering can take place either with the oxygen flow or from a separate metering device. In order to achieve a high reaction rate, intensive mixing of gas and liquid is necessary. Working under pressure is also possible.

Geeignete Lösungsmittel für die Oxidation sind z. B.:

  • Methylenchlorid, Chloroform, Tetrachlorkohlenstoff, Chlorbenzol, Dichlorbenzol, Benzol, Toluol, Xylol, Cumol, Essigsäure, Propionsäure, Milchsäure, Dichloräthan, Methanol, Äthanol, Propanol, Isopropanol, Butanol, Glykol, Methylglykol, Dimethylglykol, Tetrahydrofuran, Dioxan, Essigester, Dimethylformamid, N-Methylpyrrolidon, Aceton oder Mischungen davon. Man kann auch in wäßriger Lösung oder Suspension oder in einem Gemisch aus Wasser und mit Wasser mischbaren Lösungsmitteln arbeiten. Der pH-Wert der Reaktionslösung sollte je nach Farbstoff im neutralen bis sauren Bereich liegen. Bevorzugt ist der saure pH-Bereich zwischen pH 1 und pH 4.
Suitable solvents for the oxidation are e.g. B .:
  • Methylene chloride, chloroform, carbon tetrachloride, chlorobenzene, dichlorobenzene, benzene, toluene, xylene, cumene, acetic acid, propionic acid, lactic acid, dichloroethane, methanol, ethanol, propanol, isopropanol, butanol, glycol, methylglycol, dimethylglycol, tetrahydrofuran, dioxane formate, dioxane formate, dioxane formate N-methylpyrrolidone, acetone or mixtures thereof. You can also work in aqueous solution or suspension or in a mixture of water and water-miscible solvents. The pH of the reaction solution should be in the neutral to acidic range depending on the dye. The acidic pH range between pH 1 and pH 4 is preferred.

Aus den deutschen Offenlegungsschriften 21 52703 und 2334918 ist die Herstellung basischer Farbstoffe durch katalytische Oxidation von Triarylmethan-Derivaten in Gegenwart von durch Fluor, Chlor, Brom, Cyan substituierter Benzochinone oder durch Nitro substituierter Phenanthrenchinone sowie von Schwermetall-Komplexen bekannt.The preparation of basic dyes by catalytic oxidation of triarylmethane derivatives in the presence of benzoquinones substituted by fluorine, chlorine, bromine, cyan or phenanthrenequinones substituted by nitro and heavy metal complexes is known from German Offenlegungsschriften 21 52703 and 2334918.

Aus der deutschen Patentschrift 2 31 992 ist die Herstellung von Farbstoffen der Triphenylmethan-Reihe durch Oxidation von Leukoverbindungen mit Nitrosylschwefelsäure bekannt.German patent specification 2 31 992 discloses the production of dyes from the triphenylmethane series by oxidation of leuco compounds with nitrosylsulfuric acid.

Aus der Lehre dieser Publikationen war das neue Verfahren nicht vorhersehbar. Es war vielmehr überraschend, daß die Verwendung von Stickstoffoxiden als Katalysatoren anstelle der Schwermetall-Komplexe der vorstehend genannten Offenlegungsschriften in ausgezeichneter Ausbeute zu Farbstoffen mit hoher Reinheit führte. Gegenüber der Verwendung der Schwermetall-Komplexe hat die Verwendung der Stickstoffoxide bzw. der Stickstoffoxid freisetzenden Verbindungen den Vorteil, daß sie das Abwasser weniger belastet.The new method was not predictable from the teaching of these publications. It was rather surprising that the use of nitrogen oxides as catalysts instead of the heavy metal complexes of the above-mentioned laid-open publications resulted in dyes with high purity in excellent yield. Compared to the use of the heavy metal complexes, the use of the nitrogen oxides or the compounds releasing nitrogen oxide has the advantage that it pollutes the waste water less.

Die folgenden Beispiele veranschaulichen die Erfindung. Die Teile beziehen sich, wenn nicht anders angegeben, auf das Gewicht.The following examples illustrate the invention. Unless otherwise stated, the parts relate to the weight.

Beispiel 1example 1

99 Teile Leukomalachitgrün, 6 Teile Chloranil und 600 Teile Eisessig werden bei 30° C intensiv mit Luft behandelt. Im Verlauf der Reaktion - Reaktionsdauer etwa 12 Stdn. - werden gleichmäßig insgesamt 1,2 Teile eines Gemisches aus Stickstoffmonoxid und Stickstoffdioxid - erzeugt durch Behandeln von Natriumnitrit mit Schwefelsäure - zudosiert. Am Ende der Reaktion sind 95% des eingesetzten Leukomalachitgrüns in Malachitgrün umgewandelt worden. Der Farbstoff wird nach Abdampfen des Eisessigs mit Natronlauge behandelt und als Carbinolbase gefällt. Nach Erwärmen der Carbinolbase mit Oxalsäure auf 70° C und Filtration fällt beim Abkühlen sehr sauberes, kristallines Malachitgrünoxalat aus. Ähnlich gute Ergebnisse erhält man, wenn man während der Luftoxidation anstelle der Stickstoffoxide gleichmäßig entweder 2,5 Teile Natriumnitrit oder 2,5 Teile Eisen-III-nitrat zusetzt.99 parts of leukomalachite green, 6 parts of chloranil and 600 parts of glacial acetic acid are treated intensively with air at 30 ° C. In the course of the reaction - reaction time about 12 hours - a total of 1.2 parts of a mixture of nitrogen monoxide and nitrogen dioxide - produced by treating sodium nitrite with sulfuric acid - are evenly metered in. At the end of the reaction, 95% of the leukomalachite green used had been converted to malachite green. After the glacial acetic acid has evaporated, the dye is treated with sodium hydroxide solution and precipitated as the carbinol base. After heating the carbinol base with oxalic acid to 70 ° C. and filtration, very clean, crystalline precipitates on cooling Malachite green oxalate. Similar good results are obtained if either 2.5 parts of sodium nitrite or 2.5 parts of iron-III-nitrate are added uniformly during the air oxidation instead of the nitrogen oxides.

Beispiel 2Example 2

Ein Gemisch von 109,5 Teilen der Verbindung der Formel

Figure imgb0014
300 Teilen Eisessig, 300 Teilen Chlorbenzol und 6 Teilen Chloranil wird bei 50°C kräftig mit Luft begast. Während der Reaktion werden kontinuierlich insgesamt 1,2 Teile eines Gemisches aus Stickstoffmonoxid und Stickstoffdioxid zudosiert. Nach vollendeter Reaktion wird das Chlorbenzol und ein Teil des Eisessigs im Vakuum abgedampft, der Rückstand in heißem H20 aufgenommen, mit verdünnter Salzsäure angesäuert, heiß filtriert und mit Natriumchlorid gefällt. Man erhält den Farbstoff in 90%iger Ausbeute. Zu ähnlichen Ergebnissen gelangt man, wenn man als Katalysatoren anstelle der Stickstoffoxide Natriumnitrit oder Eisen-III-nitrat verwendet.A mixture of 109.5 parts of the compound of the formula
Figure imgb0014
 300 parts of glacial acetic acid, 300 parts of chlorobenzene and 6 parts of chloranil are gassed with air at 50 ° C. A total of 1.2 parts of a mixture of nitrogen monoxide and nitrogen dioxide are metered in continuously during the reaction. When the reaction is complete, the chlorobenzene and part of the glacial acetic acid are evaporated off in vacuo, the residue is taken up in hot H 2 O, acidified with dilute hydrochloric acid, filtered hot and precipitated with sodium chloride. The dye is obtained in 90% yield. Similar results are obtained if sodium nitrite or iron (III) nitrate is used as the catalyst instead of the nitrogen oxides.

Beispiel 3Example 3

Eine Suspension von 31,8 Teilen der Verbindung der Formel

Figure imgb0015
1 Teil Chloranil und 450 Teilen Wasser wird unter starkem Rühren bei 70° C mit Sauerstoff behandelt. Während der Reaktion werden kontinuierlich insgesamt 0,5 Teile eines Gemisches aus Stickstoffmonoxid und Stickstoffdioxid zudosiert. Am Ende der Reaktion sind 88% der eingesetzten Ausgangsverbindung zum Farbstoff oxidiert. Der Farbstoff kann durch Behandeln der Reaktionslösung mit Natriumchlorid isoliert werden. Ähnliche Ergebnisse erhält man, wenn man anstelle der Stickstoffoxide Natriumnitrit oder Eisen-III-nitrat als Katalysatoren einsetzt.A suspension of 31.8 parts of the compound of the formula
Figure imgb0015
 1 part of chloranil and 450 parts of water are treated with oxygen at 70 ° C. with vigorous stirring. A total of 0.5 part of a mixture of nitrogen monoxide and nitrogen dioxide is metered in continuously during the reaction. At the end of the reaction, 88% of the starting compound used is oxidized to the dye. The dye can be isolated by treating the reaction solution with sodium chloride. Similar results are obtained if sodium nitrite or iron (III) nitrate are used as catalysts instead of the nitrogen oxides.

Beispiel4Example4

107 Teile Leukodiamantgrün und 6 Teile Chloranil werden in 60 Teilen Eisessig und 500 Teilen Chloroform gelöst. Diese Lösung wird bei 30°C intensiv mit Luft begast. Im Verlauf der Reaktion werden insgesamt 1,2 Teile eines Gemisches aus Stickstoffmonoxid und Stickstoffdioxid zudosiert. Nach beendeter Reaktion enthält die Reaktionslösung Diamantgrün in 92%iger Ausbeute.107 parts of leuco diamond green and 6 parts of chloranil are dissolved in 60 parts of glacial acetic acid and 500 parts of chloroform. This solution is gassed intensively with air at 30 ° C. In the course of the reaction, a total of 1.2 parts of a mixture of nitrogen monoxide and nitrogen dioxide are metered in. After the reaction has ended, the reaction solution contains diamond green in 92% yield.

Beispiel 5Example 5

118 Teile der Verbindung der Formel

Figure imgb0016
und 6 Teile Chloranil werden in 60 Teilen Eisessig und 500 Teilen Chloroform gelöst. Bei 50 C wird in diese Lösung unter intensivem Rühren Luft eingeleitet. Gleichzeitig werden mit dem Luftstrom insgesamt 1,2 Teile eines Gemisches aus Stickstoffmonoxid und Stickstoffdioxid zudosiert. Nach beendeter Reaktion wird im Vakuum das Chloroform eingedampft, der Rückstand mit warmem Wasser aufgenommen, filtriert und mit Natriumchloridlösung ausgesalzen. Man erhält den Farbstoff in 87%ig. Ausbeute.118 parts of the compound of the formula
Figure imgb0016
 and 6 parts of chloranil are dissolved in 60 parts of glacial acetic acid and 500 parts of chloroform. At 50 C, air is introduced into this solution with vigorous stirring. At the same time, a total of 1.2 parts of a mixture of nitrogen monoxide and nitrogen dioxide are metered in with the air stream. When the reaction is complete, the chloroform is evaporated in vacuo, the residue is taken up in warm water, filtered and salted out with sodium chloride solution. The dye is obtained in 87%. Yield.

Nach dem erfindungsgemäßen Verfahren lassen sich die folgenden Leukoverbindungen ebenfalls in guter Ausbeute oxidieren.

Figure imgb0017
Figure imgb0018
Figure imgb0019
Figure imgb0020
Figure imgb0021
 The following leuco compounds can also be oxidized in good yield by the process according to the invention.
Figure imgb0017
Figure imgb0018
Figure imgb0019
Figure imgb0020
Figure imgb0021

Claims (4)

1. Process for the preparation of basic dyestuffs of the general formula
Figure imgb0035
in which
A and B independently of one another represent a hetero-aromatic radical or a radical of the general formula
Figure imgb0036
in which
Ar denotes the groupings
Figure imgb0037
in which
Y represents hydrogen or non-ionic substituents and
n represents a number between 1 and 4, and
R1 and R2 represent hydrogen or alkyl which is optionally substituted by non-ionic or acid groups, aryl, cyclohexyl or aralkyl or together, or with the o-position of Ar, form a heterocyclic ring which can be substituted by C1 ― C4 alkyl or phenyl,
D denotes hydrogen, alkyl, aryl which is optionally substituted by neutral or acid groups, or a heteroaromatic radical and
X represents an anion,

characterised in that compounds of the general formula
Figure imgb0038
in which
A, B and D have the abovementioned meaning,

are oxidised with oxygen in the presence of catalytic amounts of benzoquinones which are substituted by halogen or cyano or of phenanthrenequinones which are substituted by nitro, an in the presence of catalytic amounts of nitrogen oxides, with the exception of dinitrogen monoxide, or of substances which produce such nitrogen oxides under the reaction conditions.
2. Process according to Claim 1, chracterised in that compounds of the general formula
Figure imgb0039
in which, independently of one another,
R3 and R5 denote hydrogen, C1- to C4-alkyl, hydroxyalkyl with two or three C atoms, cyanoethyl, alkoxyalkyl with a total of three to five C atoms, alkoxycarbonylalkyl with a total of three to eight C atoms, alkylcarbonyloxyalkyl with a total of three to eight C atoms, C1- to C4-halogenoalkyl, sulphoalkyl with two to four C atoms, cyclohexyl, benzyl, phenyl, phenethyl, phenyl which is substituted by halogen or C1- to C4-alkyl or -alkoxy, or sulphobenzyl,
R4 and R6 denote Cl- to C4-alkyl, hydroxyalkyl with two or three C atoms, cyanoethyl, C1- to C4-halogenoalkyl, alkoxyalkyl with a total of three to five C atoms, alkoxycarbonylalkyl with a total of three to eight C atoms, alkylcarbonyloxyalkyl with a total of three to eight C atoms or benzyl or
R3 and R4 and/or R5 and R6 together form a pyrrolidine, piperidine, morpholine or piperazine ring which is optionally substituted by C1-C4-alkyl, or
R3, R4, R5 and/or R6 are linked to the o-position of the phenyl ring and then with the phenyl ring together form a tetrahydroquinoline, indoline, julolidine, phenomor coline, tetrahydro- quinoxaline or carbazole ring which is optionally substituted by C1-C4-alkyl, phenyl or benzyl,
R7 and R8 represent hydrogen, C1- to C4-alkyl, C1-to C4-alkoxy, carboxylic acid or halogen,
n denotes an integer between 1 and 4 and
E denotes phenyl, phenyl or naphthyl which is mono-substituted or disubstituted by halogen, C1- to C4-alkyl, C1- to C4-alkoxy, nitro, the carboxyl group or the sulphonic acid group, a heterocyclic radical of the general formula V
Figure imgb0040
in which
Rg denotes H, C1―C4-alkyl, phenyl, carboxylic acid C1- or C2-alkyl ester, carboxylic acid amide which is optionally N-substituted by C1-C4-alkyl, or C1―C4-alkoxy, or
E denotes a radical of the general formulae
Figure imgb0041
in which
n, R3, R4 and R7 have the abovementioned meaning, or
E denotes a radical of the general formulae
Figure imgb0042
in which
Rio denotes hydrogen, C1-C4-alkyl or halogen, in particular chlorine or bromine, and n, R3, R4, R5, R6, R7, R8 und X- have the abovementioned meaning,

are prepared by oxidising compounds of the general formula
Figure imgb0043
in which
n and R3 to R8 hav the abovementioned meaning and
F Fis the same as E or is a radical of the general formulae
Figure imgb0044
in which
n, R3to R8 and R10 have the abovementioned meaning,

with oxygen in the presence of catalytic amounts of nitrogen monoxide, nitrogen dioxide, sodium nitrite or iron-III nitrate.
3. Process according to Claim 1, chracterised in that compounds of the formula in Claim 2, wherein
R3 and R5 represent hydrogen, methyl, ethyl, hydroxyethyl, propyl, cyanoethyl or butyl,
R4 and R6 represent methyl, ethyl, sulphobenzyl or sulphoethyl,
R7 and R8 represent hydrogen, methyl, methoxy and chlorine,
E represents phenyl, phenyl which is substituted by chlorine, methoxy or the sulphonic acid group, p-dimethylaminophenyl, p-diethylaminophenyl, p-bis-hydroxyethylamino- phenyl or the radical of the general formula
Figure imgb0045
m which
R represents hydrogen, methyl or phenyl and
R3 represents methyl or phenyl, and
n and X have the meanings given in Claim 2,

are prepared by oxidising corresponding triarylmethane derivatives with oxygen in the presence of catalytic amounts of tetrachloro- or tetrabromo-1,4-benzoquinone and catalytic amounts of nitrogen monoxide and/or nitrogen dioxide.
EP79104781A 1978-12-13 1979-11-30 Process for preparing basic dyestuffs Expired EP0012283B1 (en)

Applications Claiming Priority (2)

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DE19782853822 DE2853822A1 (en) 1978-12-13 1978-12-13 METHOD FOR PRODUCING BASIC DYES
DE2853822 1978-12-13

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EP0012283B1 true EP0012283B1 (en) 1981-09-23

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DE2928404A1 (en) * 1979-07-13 1981-01-29 Bayer Ag METHOD FOR PRODUCING BASIC DYES
DE2928466A1 (en) * 1979-07-13 1981-01-29 Bayer Ag METHOD FOR PRODUCING CATIONIC DYES
DE3261213D1 (en) * 1981-01-22 1984-12-20 Ciba Geigy Ag Process for the production of leuco triaryl methane compounds
US4536368A (en) * 1983-12-09 1985-08-20 The Hilton-Davis Chemical Co. Method for sanitizing toilets
US4536367A (en) * 1983-12-09 1985-08-20 The Hilton-Davis Chemical Co. Method for sanitizing toilets
EP0144958A3 (en) * 1983-12-09 1986-07-09 The Hilton - Davis Chemical Company Method of flushing
EP0174371B1 (en) * 1984-03-02 1990-09-19 Wako Pure Chemical Industries, Ltd. Triphenylmethane derivatives and method for determining oxidative substances using them as color-forming component
US5194390A (en) * 1988-07-05 1993-03-16 Miles Inc. Composition for the assay of albumin
DE3842014A1 (en) * 1988-12-14 1990-06-21 Bayer Ag METHOD FOR PRODUCING SULFOGROUPLE-FREE TRIPHENYLMETHANE DYES
EP0558450B1 (en) * 1992-02-28 1999-03-17 Ciba SC Holding AG Process for dyeing leather with mixtures of dyes
US5486213A (en) * 1992-06-30 1996-01-23 Ciba-Geigy Corporation Process for the dyeing of leather with dye mixtures
US8163074B2 (en) * 2007-02-06 2012-04-24 Xerox Corporation Phase change inks containing colorant compounds
US7910754B2 (en) 2007-02-06 2011-03-22 Xerox Corporation Colorant compounds
US7736426B2 (en) * 2007-02-06 2010-06-15 Xerox Corporation Phase change inks containing colorant compounds

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BE787210A (en) * 1971-08-04 1973-02-05 Basf Ag PROCESS FOR THE CATALYTIC OXIDATION OF DI- AND TRI- (HETERO) -ARYL-METHANE COMPOUNDS

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